JPH0214232A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition having durable antistatic effect and excellent impact resistance, permanence of molded article, weld strength and moldability by compounding specific amounts of two specific kinds of styrene copolymer resins and a polyether (ester) amide. CONSTITUTION:The objective resin composition is produced by compounding (A) 22-45wt.% of a rubber-reinforced styrene copolymer resin containing 0.1-10wt.% of a carboxyl-containing unsaturated compound as a copolymerized component, (B) 50-77wt.% of a (rubber-reinforced) styrene copolymer resin free from carboxyl-containing unsaturated compound as a copolymerized component and (C) 1-26wt.% of a polyether amide and/or polyether ester amide. The amount of the carboxyl-containing unsaturated compound of the component A is 0.02-40wt.% based on the sum of the components A, B and C. The average grafting ratio of the rubber component in the components A and B is >=20wt.% and the intrinsic viscosity of an acetone-soluble component is >=0.35dl/g.

Description

[Detailed description of the invention] a. Industrial application field The present invention relates to a novel thermoplastic resin composition.

More specifically, the present invention relates to a thermoplastic resin composition that has a long-lasting antistatic effect and has excellent impact resistance, molded appearance, weld strength, and molding processability.

b. Prior Art When synthetic polymer materials (hereinafter referred to as resins) are used for electrical and electronic equipment parts, their antistatic effect becomes a problem. That is, when these resin molded products are charged with electric charge, the performance of electrical and electronic functions is adversely affected by the electric charge. Further, the commercial value may be significantly reduced due to the adhesion of dust. In order to improve these problems, antistatic agents are mixed in or coated. According to this, - although it has a temporal effect,
The drawback is that the effect does not last for a long time.

JP-A No. 60-23435 discloses an antistatic property obtained by mixing (AI) 5 to 80% by weight of polyether ester amide and (Bl) 95 to 20% by weight of a modified vinyl polymer containing a carboxyl group. A resin composition is disclosed. Example 2 of the same publication includes the above (AI) and (Bl).
In addition, 25% by weight of ABS resin (polymer C = 4)
and 30% by weight, and the Izot impact strength (notched) of these resin compositions is described to be 10 to 12 kgcm/cm.

JP-A-62-241945 discloses (A2) 1 to 40 parts by weight of polyether ester amide, (B2) 5 to 98 parts by weight of ABS-based graph graft copolymer, and (C2) modified vinyl-based material containing a carboxyl group. A thermoplastic resin composition comprising 0.1 to 20 parts by weight of a polymer is disclosed.

The above-mentioned publication discloses that the thermoplastic resin composition has excellent moldability, no delamination, and an excellent surface appearance.

JP-A No. 62-241945 includes JP-A No. 60-2
It is stated that the disadvantages of the composition of No. 3435 are that the compounded amount of the carboxyl group-containing modified vinyl polymer is high, resulting in poor moldability and poor reproducibility of physical properties. Experiments conducted by the present inventors also revealed that the Izot impact strength, fluidity, molded appearance, etc. were poor.

It is believed that this is related not only to the large amount of the carboxyl group-containing modified vinyl polymer blended, but also to the small amount of the ABS resin as the third component.

These drawbacks are considerably improved in JP-A-62-241945 by reducing the amount of the carboxyl group-containing modified vinyl polymer and increasing the amount of the third component, ABS resin.

However, there is a drawback that the weld strength decreases due to the weight loss of the carboxyl group-containing modified vinyl polymer.

Problems to be Solved by the C0 Invention An object of the present invention is to provide a novel thermoplastic resin composition having an antistatic effect.

Another object of the present invention is to provide a thermoplastic resin composition that has an antistatic effect, is excellent in molding processability and molded appearance, and also has excellent impact resistance and weld strength in a well-balanced manner. .

Yet another object of the present invention is to provide a thermoplastic resin composition that has both excellent impact resistance and weld strength, and has an antistatic effect that has not been achieved by the prior art.

Further objects and advantages of the present invention will become apparent from the description below.

Means and operation for solving the d1 problem According to the present invention, the objects and advantages of the present invention are as follows: (A) a rubber-reinforced styrenic copolymer resin containing a carboxyl group-containing unsaturated compound as a copolymerization component; (B) A rubber-reinforced or non-reinforced styrenic copolymer resin that does not contain a carboxyl group-containing unsaturated compound as a copolymerization component, and (C) a resin that contains at least one of polyetheramide and polyetheresteramide. , and (D) based on the total amount of components (A), (B), and (C) above, component (A) is in the range of 22 to 45% by weight, and component (B) is in the range of 50 to 77% by weight. and (C) component is in the range of 1 to 26% by weight, and (E) the content of the carboxyl group-containing compound in the (A) component resin is 0°1- based on component (A). in the range of 10% by weight and in the range of 0.02 to 4% by weight based on the total amount of components (A), (B) and (C), (F) the rubber component in the resin component (A) Or above (
When the component resin B) contains a rubber component, the average grafting rate of the rubber components in the component resins (A) and (B) is at least 20% by weight, and the intrinsic viscosity of the acetone soluble portion ( (30°C, in methyl ethyl ketone) is at least 0.35 dff/g, and (G) the content of the rubber component is 5 to 40% by weight based on the total amount of components (A), (B) and (C) above. % of the thermoplastic resin composition.

As described above, the thermoplastic resin composition of the present invention (hereinafter sometimes referred to as the composition of the present invention) contains the three components (A), (B), and (C) as essential components. As described in (D) to (G), it is characteristic in that the polymer composition is strictly specified.

Rubber-reinforced styrenic copolymer resin containing the carboxyl group-containing unsaturated compound of component (A) as a copolymerization component (
(hereinafter sometimes referred to as (A) component resin), the carboxyl group-containing compound contained as a copolymerization component is used as a constituent component of the rubbery polymer of (1) rubber-reinforced styrenic copolymer (2). ) as a graft component of a rubber-reinforced styrenic copolymer to a rubbery polymer, or (3)
It can be any resin contained as a component of the matrix polymer portion of the rubber-reinforced styrenic copolymer.

Among these, the resin containing the carboxyl group-containing compound as a copolymerization component in the embodiment (1) or (2) above gives the composition of the present invention particularly high impact strength and weld strength, and has good properties. Because it gives a molded appearance,
preferable.

Examples of rubbery polymers include ethylene-propylene random copolymers and block copolymers, and ethylene-propylene random copolymers and block copolymers.
Copolymers of ethylene and a-olefins, such as random and block copolymers of butene;
Copolymers of ethylene and unsaturated carboxylic acid esters such as methacrylate and ethylene-butyl acrylate; Copolymers of ethylene and vinyl fatty acids such as ethylene-vinyl acetate; ethylene-propylene-ethylidene norhorne copolymers, ethylene- Ethylene-propylene-nonconjugated genterpolymers such as propylene-hexadiene copolymers: random and block copolymers of polybutadiene, isoprene, styrene-butadiene;
Furthermore, a hydrogenated product of the block copolymer; acrylonitrile-
Examples include diene rubbers such as butadiene copolymers and butadiene-isoprene copolymers; butylene-isogrene copolymers.

These rubbery polymers can be used alone or in combination of two or more.

Among these, preferable rubbery polymers in terms of impact resistance and the like are diene rubber, ethylene-propylene rubber, and ethylene-propylene-nonconjugated genter polymer, and more preferably polybutadiene and styrene content of 50% by weight or less. It is a styrene-butadiene copolymer.

Examples of the carboxyl group-containing unsaturated compound include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, itaconic acid, and maleic acid. Among these, acrylic acid and methacrylic acid are preferred.

The carboxyl group-containing unsaturated compounds can be used alone or in combination of two or more.

The rubber-reinforced styrenic copolymer of the present invention can be produced by, for example, polymerizing a carboxyl group-containing compound, a styrene compound, and, if necessary, other copolymerizable monomers in the presence of a rubbery polymer. can be manufactured.

Examples of styrenic compounds include styrene, a-methylstyrene, methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, ptert-7'tylstyrene,
Examples include ethylstyrene, vinylnaphthalene, 0-methylstyrene, p-methylstyrene, and dimethylstyrene.

These styrene compounds can be used alone or in combination of two or more. As the styrene compound, styrene and a combination of 50% by weight or more of styrene and other styrene compounds are particularly preferred.

Examples of other copolymerizable monomers that can be used as necessary include maleimide compounds, vinyl cyan compounds, and other vinyl monomers copolymerizable with these compounds.

Examples of maleimide compounds include maleimide, N-
Methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-o-chlorophenylmaleimide, N
-Cyclohexylmaleimide and the like. Particularly preferred are N-7 enylmaleimide, N-o-chlorophenylmaleimide, N-cyclohexylmaleimide, and the like.

These may be used alone or in combination of two or more.

Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile, and among these, acrylonitrile is preferred.

Other copolymerizable vinyl compounds include, for example, acrylic acid alkyl esters such as methyl acrylate, ethyl acrylate, and propylene acrylate; methacrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, and propylene methacrylate;
Examples include unsaturated acid anhydrides such as maleic anhydride, itaconic anhydride, and citraconic anhydride. Even one of these two
More than one species may be used in combination.

The above (A) component resin used in the composition of the present invention contains a carboxyl group-containing unsaturated compound as a copolymerization component,
Contained in an amount ranging from 0.1 to IO weight % based on the component resin (A) and from 0.02 to 4 weight % based on the total amount of components (A), (B), and (C). . If the amount falls below the lower limit of either range, the resulting composition will have poor impact resistance and weld strength retention, while if the amount exceeds the upper limit, the resulting composition will have poor impact resistance, weld strength, and molded appearance.

In the composition of the present invention, the component resin (A) preferably contains a carboxyl group-containing unsaturated compound as a copolymerization component, based on the component resin (A), preferably 0.2 to 9% by weight, more preferably 0. .2 to 8% by weight, and (A), (B
) and (C), preferably 0.
The content is preferably 0.02 to 3.5% by weight, more preferably 0.02 to 3% by weight.

Component (B) of the composition of the present invention is a rubber-reinforced or non-reinforced styrenic copolymer resin (hereinafter sometimes referred to as CB component resin) that does not contain a carboxyl group-containing compound as a copolymerization component.

The component resin (B) can be produced, for example, by polymerizing a styrene compound and, if necessary, other copolymerizable monomers in the presence or absence of a rubbery polymer.

As the styrene compound, the same compounds as described for the resin component (A) above can be used.

Other copolymerizable monomers include, for example, maleimide compounds, vinyl cyanide compounds, and other copolymerizable vinyl monomers, and these examples are also as described for the component resin (A) above. be.

(B) The component resin is a polymer obtained by polymerizing a styrene compound and other copolymerizable monomers as necessary in the presence of a rubbery polymer, or a polymer obtained by polymerizing a styrene compound and other monomers that can be copolymerized as necessary, in the absence of a rubbery polymer. It can be either a polymer obtained by polymerizing the above-mentioned hexamer or a mixture of these polymers.

(B) Component resins include, for example, acrylonitrile-butadiene rubber-styrene resin (ABS resin), acrylonitrile-ethylenepropylene rubber-styrene resin (A
ES resin), acrylonitrile-styrene copolymer (A
S resin), methyl methacrylate-styrene copolymer (M
S resin), high impact polystyrene (HIPS),
Examples include acrylonitrile-〇-butyl acrylate rubber-styrene resin (AAS resin).

The rubber components in the (A) component resin and (B) component resin of the present invention both have a grafting rate of at least 20% by weight and an acetone soluble content of at least 0.35 dI2/g (methyl ethyl ketone solvent, at 30°C). It has an intrinsic viscosity of (measured).

When the grafting rate is less than 20% by weight, the gloss of the composition is affected by the molding temperature, resulting in low gloss, uneven appearance, and poor molded appearance.

Grafting ratio is defined by the following measurement method.

Accurately weigh 1 g of sample, add 20 cc of acetone to it, shake for 10 hours, and then rotate at 20°000 rpm.
A soluble fraction and an insoluble fraction are separated using a centrifugal separator, and the insoluble fraction is dried using a vacuum dryer to obtain an insoluble fraction (C). on the other hand,
From the polymerization composition and polymerization conversion rate, the amount of rubber (R
) is calculated.

Calculate the grafting rate using the following formula.

The grafting rate of the rubber component is preferably at least 25% by weight, more preferably from 30 to 150% by weight.

If the intrinsic viscosity of the acetone soluble component is less than 0.35 dQ/g, the resulting composition will have low impact resistance and weld strength. The intrinsic viscosity of the acetone soluble component is preferably 0.
．． 37dQ/g-1, OdQ/g.

Further, the rubber component is contained in an amount of 5 to 40% by weight based on the total amount of components (A), (B), and (C) of the composition of the present invention.

If it is less than 5% by weight, the resulting composition will have low impact resistance and weld strength, and if it exceeds 40% by weight, the resulting composition will have poor moldability and poor molded appearance.

The rubber component is preferably contained in an amount of 5 to 35% by weight, more preferably 6 to 30% by weight, based on the same criteria.

Component (C) of the composition of the present invention is at least one of polyether amide and polyether ester amide. Polyetheramide and polyetheresteramide are block copolymers having polyether as a soft segment and polyesteramide or polyamide as a hard segment, and can be produced by a known method.

The polyesteramide portion and the hard segment which is the polyamide portion are formed, for example, from a salt of an aminocarboxylic acid or lactam having 6 or more carbon atoms or a diamine having 6 or more carbon atoms and a carboxylic acid.

Examples of these include, for example, ω-aminocaproic acid, ω
-aminoenantoic acid, ω-aminocapric acid, ω-aminopergonic acid, 1,1-aminoundecanoic acid and 12
- Aminocarboxylic acids such as aminododecanoic acid or lactams such as caprolactam, enantholactam, capryllactam and laurolactam and hexamethylene diamine - adipate, hexamethylene diamine -
Mention may be made of salts of diamine-dicarboxylic acids such as sebacate and hexamethylene diamine-isophthalate. Among these, hexamethylene diamine adipate is particularly preferably used.

The soft segment which is a polyether moiety is, for example, polyethylene glycol, poly(1,2-propylene oxide) glycol, poly(l,3-propylene oxide) glycol, poly(tetramethylene oxide) glycol, poly(hexamethylene oxide) glycol. , a block or random copolymer of ethylene oxide and propylene oxide, and a block or random copolymer of ethylene oxide and tetrahydro-7 run.

Among these, polyethylene glycol is particularly preferred since it has excellent antistatic properties.

The number average molecular weight of these poly(alkylene oxide) glycols is preferably 200 to aooo.

Particularly preferably, the temperature is in the range of 250 to 300 degrees.

At this number average molecular weight, a polyether amide or polyether ester amide with particularly excellent antistatic effect and excellent mechanical properties can be obtained.

The dicarboxylic acid component constituting the polyether ester amide is preferably a dicarboxylic acid having 4 to 2 degrees of carbon atoms. Examples include terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4-dicarboxylic acid.
'-dicarboxylic acids, aromatic dicarboxylic acids such as diphenoxyethanedicarboxylic acid and sodium 3-sulfoisophthalate, l,4-cyclohexanedicarboxylic acid, 1
．． Included are aliphatic dicarboxylic acids such as 2-cyclohexanedicarboxylic acid and fatty acid dicarboxylic acids such as succinic acid, oxalic acid, adipic acid, sebacic acid, and dodecanedioic acid.

In particular, terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, sebacic acid and dodecanedioic acid are preferably used from the viewpoint of polymerizability, color tone and physical properties.

The composition of the present invention contains the above (A), (B), and (C) component resins, and based on the total amount thereof, a rubber-reinforced styrenic resin containing a carboxyl group-containing unsaturated compound as a copolymer component. Copolymer resin [(A) component 1 is 22~
The content of the styrene copolymer resin as component (B) is 50 to 77% by weight, and the content of component (C) is 1 to 26% by weight.

If the component (A) does not reach the lower limit, the resulting composition will have low impact resistance and weld strength, and if it exceeds the upper limit,
The impact resistance, weld strength, and molded appearance of the resulting composition deteriorate. The content of component (A) is preferably 22 to 43% by weight, more preferably 24 to 40% by weight.

If component (B) does not reach the lower limit, the resulting composition will have low impact resistance, while if it exceeds the upper limit, the weld strength of the resulting composition will decrease. The amount of component (B) is preferably 50 to 75% by weight, more preferably 55 to 70% by weight.

Furthermore, if the content of component (C) does not reach the lower limit, the antistatic effect and moldability of the resulting composition will deteriorate, while if it exceeds the upper limit, the rigidity and heat resistance of the resulting composition will decrease.

The amount of component (C) is preferably 3 to 25% by weight, more preferably 5 to 25% by weight.

(A), (B), (C) when producing the composition of the present invention
Conventional methods are used for mixing the ingredients.

For example, after mixing each component with a mixer, 2
The mixture is melt-kneaded and granulated at 00 to 320°C.

More simply, each component can be directly melt-kneaded and molded in a molding machine.

The compositions of the present invention include antioxidants such as 2,6-di-t-butyl-4-methylphenol, 2-(l-methylcyclohexyl)-4,6-dimethylphenol, 2,2-methylene-bis-( 4-ethyl-6-t-butylphenol), tris(dinonylphenyl)phosphite; -hydroxy-4'-n-octoxyphenyl)benzotriazole; lubricants such as paraffin wax, stearic acid, hydrogenated oils, stearamide,
Methylene bisstearamide, n-butyl stearate ketone wax, octyl alcohol, hydroxystearic triglyceride; flame retardants such as antimony oxide, aluminum hydroxide, zinc oxalate, tricresyl phosphate, tris(dichloropropyl) phosphate,
Chlorinated paraffins, tetrabromobutane, hexabromobenzene, tetrabromobisphenol A; antistatic agents such as steroamidoprobyl dimethyl-β-hydroxyethylammonium nitrate; colorants such as titanium oxide, carbon black; fillers such as Calcium carbonate, clay, silica, glass fibers, glass spheres, carbon fibers, pigments, etc. can be added as necessary.

e. Examples Next, the present invention will be explained in more detail with reference to Examples.

Production Example 1 (Production of rubber-reinforced styrenic copolymer copolymerized with carboxyl group-containing unsaturated compound) = (1) Production method of rubbery polymer: Stainless steel polymerization machine with internal volume of 100Q equipped with four-stage paddle blades A polymerization reaction was carried out according to the recipe shown in Table 1 using a reactor. Raise the temperature while stirring at a rotation speed of 9 Orpm with paddle blades,
When the temperature reached 50°C, potassium persulfate was added, and thereafter the polymerization reaction was carried out while controlling the reaction temperature to be kept constant at 50°C. When the polymerization rate reached 90%, diethyl hydroxyl was added. The reaction was stopped by adding 0.1 part by weight of amine, and the unreacted slag was substantially distilled off by steam distillation to obtain a rubbery latex.

Table 1 (2) Method for producing carboxyl group-containing unsaturated compound copolymerized graft copolymer: In a 7I2 glass flask equipped with a stirring blade, 100 parts of ion-exchanged water and 0 parts of sodium dodecylbenzenesulfonate were added.
．． Add 5 parts of potassium hydroxide, 0.01 part of potassium hydroxide, 0.1 part of butane, and batch polymerization components consisting of the rubbery polymer latex and various monomers in Table 1 in the proportions shown in Table 2, and stir. Do not raise the temperature while doing so. When the temperature reached 45°C, 0.1 part of ethylenediaminetetraacetic acid sodium salt,
Add 0.003 parts of ferrous sulfate, 0.2 parts of formaldehyde sodium sulfoxylate dihydrate, and 15 parts of ion-exchanged water and 0.1 part of diisopropylbenzene hydroperoxide. The reaction continued for hours. Thereafter, 50 parts of ion-exchanged water, 1 part of sodium dodecylbenzene sulfonate, 0.02 part of potassium hydroxide, 0.1 part of t-dodecylmercaptan, 0.2 part of diisopropylbenzene hydroperoxide and various amounts of the proportions shown in Table 2 were added. The reaction was continued by continuously adding 1/2 increment mixture of monomers over a period of 3 hours. After the addition was completed, the reaction was continued for 1 hour while stirring, and then 0.2 parts by weight of 2,2-methylene-bis-(4-ethyl-6-t-butylphenol) was added.
The reaction product was taken out from the flask. potassium chloride 2
The product was coagulated using parts by weight, and the powdered graft resin was recovered by dehydration, washing with water, and drying. Table 2 shows the seven-mer polymerization conversion rate and the graft rate intrinsic viscosity [η] measured by the method described above.

Table 2 In a similar way, Table 3 with the prescription shown in Table 3 (polymerization body composition) A polymer was obtained.

(3) Production of styrenic copolymer resin containing no carboxyl group-containing compound: In the same manner as described in (2) above, the polymers listed in Table 4 were obtained using the formulations listed in Table 4. .

Table 4 (4) The following polyether amide and polyether ester amide were prepared.

Polyetheramide: obtained from 50 parts of caprolactam and 50 parts of polyethylene glycol having a number average molecular weight of 1000.

Polyether ester amide: 50 parts of caprolactam,
It was obtained from 40 parts of polyethylene glycol having a number average molecular weight of 1000 and 7 parts of adipic acid.

Examples 1 to 7, Comparative Examples 1 to 8 Each component shown in Table 6 was heated at a temperature of 23 cm using a 40 m/m extruder.
Create pellets by melting and kneading at 0°C.

The pellets were molded using a 50z injection molding machine (Toshiba Corporation l5-
8OA) at a molding temperature of 240°C to create a test piece.

Impact strength Izot impact strength (ASTM D256, notched 1/4 #thickness), falling weight strength (2.4 m/thickness) A 5 kg impacting body (diameter 11 nch) was dropped from 1 m onto a test piece and destroyed. (Determine the energy) was measured.

Weld Strength The tensile strength (Tw) was measured using a test piece molded using a mold with a weld line in the center of an ASTMI dumbbell, and then the tensile strength was measured using a test piece molded using a mold without a weld line. (T o ) is measured. (Tw/T
o) Weld strength (retention rate) was determined at X 100%.

Molding Appearance: A test piece measuring 20 cm x 20 cm x 2°4 mm was molded using a 50z injection molding machine, and its glossiness was measured.

Surface resistivity was measured using a surface resistance meter (Mitsubishi Yukabu, H1resta).

Charge decay rate 5Latic Honestometer (S HI
S I Do Co.

A voltage of 8 kV was applied to the test piece for 1 minute using the Ltd), and then the voltage was removed to measure the amount of charge, and the time required for it to become half of the initial value was measured.

This was taken as the half-life value (5 ec). The smaller this value is, the better the antistatic property is.

f9 Effects of the Invention As is clear from the above, the present invention can provide a thermoplastic resin composition that has a long-lasting antistatic effect and is excellent in impact resistance, weld strength, and molded appearance. Furthermore, the obtained thermoplastic resin composition has a high level of balance in various physical properties, and is an excellent resin material that can meet recent strict quality requirements.

1 other person

Claims (1)

[Claims] 1. (A) Rubber-reinforced styrenic copolymer resin containing a carboxyl group-containing unsaturated compound as a copolymerization component; (B) Rubber not containing a carboxyl group-containing unsaturated compound as a copolymerization component. a reinforced or non-reinforced styrenic copolymer resin; (C) at least one of polyether amide and polyether ester amide; and (D) the above (A), (B) and (C). Based on the total amount of ingredients, component (A) is in the range of 22 to 45% by weight, component (B) is in the range of 50 to 77% by weight, and component (C) is in the range of 1 to 26% by weight. (E) The content of the carboxyl group-containing compound in the (A) component resin is 0.1 to 10% by weight based on the (A) component.
and in the range of 0.02 to 4% by weight based on the total amount of components (A), (B) and (C), B)
When the component resin contains a rubber component, the average grafting rate of the rubber component in the component resin (A) and the component resin (B) is at least 20% by weight, and the intrinsic viscosity of the acetone soluble portion (30°C , in methyl ethyl ketone) is at least 0
．． 35 dl/g, and (G) the content of the rubber component is in the range of 5 to 40% by weight based on the total amount of the above components (A), (B), and (C). Thermoplastic resin composition.